Zirconium and zirconium alloy quantitative hydrogen content hydrogenation method and hydrogenation parts

Abstract

The embodiment of the present application provides a method for hydrogenating zirconium and zirconium alloys with quantitative hydrogen content and a hydrogenated part, the method comprising: heating the zirconium or zirconium alloy sample to a first temperature for degassing under a first vacuum condition; introducing a protective gas, and placing the zirconium or zirconium alloy sample in a protective gas atmosphere of a first pressure under a second temperature condition; introducing a certain amount of pure hydrogen, and when the pressure returns to the first pressure, introducing a certain amount of pure hydrogen again, and repeating the hydrogenation process multiple times until the total amount of pure hydrogen introduced reaches the target hydrogen content, and the temperature of the multiple hydrogenation processes is maintained at the second temperature. The method for hydrogenating zirconium and zirconium alloys with quantitative hydrogen content according to the embodiment of the present application can accurately control the amount of hydrogenation.

Description

Technical Field

[0001] The present invention belongs to the technical field of zirconium and zirconium alloy performance research, and in particular, relates to a method for hydrogenating zirconium and zirconium alloys with quantitative hydrogen content and a hydrogenated component. Background Art

[0002] Zirconium alloy has the advantages of small thermal neutron absorption cross-section, high thermal conductivity, good resistance to water side corrosion and high mechanical strength. It is widely used as reactor inner cladding material and core structure material.

[0003] Zirconium is active to hydrogen. It absorbs hydrogen at a temperature where it does not react with oxygen. Therefore, zirconium can be used as a hydrogen storage material. Its maximum hydrogen absorption is equivalent to ZrH1.93. Zirconium alloys absorb hydrogen as a result of corrosion reaction with water. Therefore, the form of zirconium and zirconium alloys in an atmosphere containing hydrogen or water vapor has important engineering significance. In water-cooled reactors, hydrogen absorption is inevitable in fuel elements that use zirconium and zirconium alloys as UO2 fuel cladding. The main sources are: hydrogen produced during the corrosion reaction, hydrogen dissolved in water and steam, hydrogen formed by radiolysis of primary water under irradiation, and hydrogen deliberately added to the cooling water in pressurized water reactors. In zirconium and zirconium alloys, the solid solubility of hydrogen is very limited. Once the solid solubility is exceeded, a zirconium hydride phase will precipitate. Since this phase is a brittle phase, especially when the temperature is below 150°C, it is more harmful and causes corrosion, hydrogen embrittlement and hydrogen blistering to zirconium and zirconium alloys. When zirconium and zirconium alloy cladding tubes operate at high temperatures, they absorb hydrides generated by corrosion reactions. The precipitation of hydrides destroys the integrity of α-Zr grains, produces microcracks, and reduces performance, especially leading to a decrease in the toughness and strength of zirconium and zirconium alloys, resulting in brittleness.

[0004] Therefore, the study of the performance of zirconium and zirconium alloys with quantitative hydrogen content after simulated irradiation has always been an important topic in the study of the application performance of zirconium and zirconium alloys. Currently, there is no method that can accurately and quantitatively control the hydrogen content. Summary of the invention

[0005] The purpose of the embodiments of the present application is to provide a method for hydrogenating zirconium and zirconium alloys with quantitative hydrogen content and a hydrogenating component, which can accurately control the amount of hydrogen permeation.

[0006] On the one hand, the present invention provides a method for hydrogenation of zirconium and zirconium alloys by quantitatively measuring hydrogen content, comprising:

[0007] The zirconium or zirconium alloy sample is heated to a first temperature for degassing under a first vacuum condition;

[0008] introducing a protective gas so that the zirconium or zirconium alloy sample is placed in a protective gas atmosphere at a first pressure under a second temperature condition;

[0009] A certain amount of pure hydrogen is introduced, and when the pressure returns to the first pressure, a certain amount of pure hydrogen is introduced again, and the hydrogenation is repeated multiple times in this cycle until the total amount of pure hydrogen introduced reaches the target hydrogen content, and the temperature of the multiple hydrogenation processes is maintained at the second temperature.

[0010] Optionally, the first vacuum degree is not greater than 1.0×10 -2 Pa.

[0011] Optionally, the first temperature is 380-450°C.

[0012] Optionally, the heating to the first temperature for degassing includes: heating to the first temperature and keeping the temperature for 10 to 25 minutes for degassing.

[0013] Optionally, the protective gas is argon.

[0014] Optionally, the first pressure is 5-13 kPa, and the second temperature is 360°C-450°C.

[0015] Optionally, the multiple hydrogen permeation is performed 3-20 times.

[0016] Optionally, the amount of pure hydrogen introduced in a single hydrogenation is 0.005 wt% to 0.0075 wt% in terms of hydrogen content.

[0017] Optionally, the volume V of pure hydrogen gas introduced in a single hydrogenation process is obtained by the following formula:

[0018]

[0019] Wherein, V is the volume of pure hydrogen introduced, ml; M is the relative molecular mass of hydrogen; A is the hydrogen content of single hydrogenation, wt%; m is the sample weight, g.

[0020] On the other hand, an embodiment of the present application provides a zirconium and zirconium alloy hydrogen-impregnated part with a quantitative hydrogen content, which is prepared by the method of any of the above embodiments.

[0021] The embodiment of the present application provides a method for hydrogenation of zirconium and zirconium alloys with quantitative hydrogen content, which introduces pure hydrogen gas multiple times to perform multiple hydrogenation operations, and determines whether a single hydrogenation is completed by measuring the pressure change during the hydrogenation process, thereby controlling the hydrogenation amount of zirconium and zirconium alloys. The present invention has high control accuracy, simple operation, and high efficiency, and can effectively prepare quantitative hydrogen content samples without changing the structure and properties of zirconium and zirconium alloys.

[0022] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present application.

[0023] The overview of various implementations or examples of the technology described in this application is not a comprehensive disclosure of the entire scope or all features of the disclosed technology. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the described embodiments of the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0025] Unless otherwise defined, the technical terms or scientific terms used in this application should be understood by people with ordinary skills in the field to which this application belongs. "First", "second" and similar words used in this application do not indicate any order, quantity or importance, but are only used to distinguish different components. "Include" or "comprise" and similar words mean that the elements or objects appearing before the word cover the elements or objects listed after the word and their equivalents, without excluding other elements or objects. "Connect" or "connected" and similar words are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "Up", "down", "left", "right" and the like are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0026] In order to keep the following description of the embodiments of the present application clear and concise, the present application omits detailed descriptions of known functions and known components.

[0027] The embodiment of the present application provides a method for hydrogenation of zirconium and zirconium alloys with quantitative hydrogen content. The purity of the gas materials involved in the embodiment of the present application, such as protective gas, pure hydrogen, etc., should meet relevant requirements. For example, the purity of the protective gas and pure hydrogen is not less than 99.999%.

[0028] A method for hydrogenation of zirconium and zirconium alloys with quantitative hydrogen content, comprising:

[0029] The zirconium or zirconium alloy sample is heated to a first temperature for degassing under a first vacuum condition;

[0030] Passing a protective gas, so that the zirconium or zirconium alloy sample is placed in a protective gas atmosphere of a first pressure under a second temperature condition;

[0031] A certain amount of pure hydrogen is introduced, and when the pressure returns to the first pressure, a certain amount of pure hydrogen is introduced again, and the hydrogenation is repeated multiple times in this cycle until the total amount of pure hydrogen introduced reaches the target hydrogen content, and the temperature of the multiple hydrogenation processes is maintained at the second temperature.

[0032] The embodiment of the present application provides a method for hydrogenation of zirconium and zirconium alloys with quantitative hydrogen content, which introduces pure hydrogen gas multiple times to perform multiple hydrogenation operations, and determines whether a single hydrogenation is completed by measuring the pressure change during the hydrogenation process, thereby controlling the hydrogenation amount of zirconium and zirconium alloys. The present invention has high control accuracy, simple operation, and high efficiency, and can effectively prepare quantitative hydrogen content samples without changing the structure and properties of zirconium and zirconium alloys.

[0033] In the embodiment of the present application, a sample of zirconium or zirconium alloy is placed in a sample chamber of a hydrogen permeation device, the sample chamber is controlled to be in a first vacuum condition, and then the temperature is increased. When the temperature reaches the first temperature, the temperature is kept for a certain period of time for degassing. During the heating and keeping temperature process, as the zirconium and zirconium alloy are degassed, the vacuum degree changes slightly, and finally the sample chamber is kept in the first vacuum condition.

[0034] In the embodiment of the present application, after vacuum degassing, protective gas is introduced into the sample chamber, the pressure in the sample chamber is controlled to be a first pressure, and the temperature of the sample chamber is controlled to be a second temperature.

[0035] A certain amount of pure hydrogen is introduced, and when the pressure returns to the first pressure, a certain amount of pure hydrogen is introduced again, and the hydrogenation is repeated multiple times in this cycle until the total amount of pure hydrogen introduced reaches the target hydrogen content, and the temperature of the hydrogenation process is maintained at the second temperature.

[0036] In the embodiment of the present application, zirconium or zirconium alloy is heated to a first temperature under a first vacuum condition for degassing, which can remove hydrogen in zirconium or zirconium alloy and reduce the influence of hydrogen in zirconium or zirconium alloy on hydrogen permeation results. In the embodiment of the present application, vacuum is first drawn and then the temperature is raised to avoid reaction between zirconium and oxygen or nitrogen, which may affect subsequent hydrogen permeation.

[0037] In some embodiments, the first vacuum degree is not greater than 1.0×10 -2 Pa. The vacuum degree in the sample chamber can be controlled to be ≤1.0×10 -2 Pa, and the vacuum degree in the sample chamber should be kept ≤1.0×10 -2 Pa will reduce the hydrogen in the zirconium alloy to below 0.001wt%, reducing the influence of hydrogen in zirconium or zirconium alloy on the hydrogen permeation result.

[0038] In some embodiments, the first temperature is 380°C to 450°C. During degassing, the sample chamber is heated to 380°C to 450°C and kept warm for a certain period of time for degassing. In an exemplary embodiment, degassing is carried out by keeping warm for 10 to 25 minutes. The maximum temperature of vacuum degassing is 450°C, which is 30°C lower than the minimum temperature of general annealing (480°C), thereby avoiding recovery and recrystallization of some zirconium alloys. The hydrogen permeation process will not change the state of the product. The minimum temperature of vacuum degassing is 380°C, which can avoid the problem of incomplete degassing and the inability to accurately control the hydrogen permeation content. The gas in the zirconium alloy can be completely removed in 10-25 minutes.

[0039] In some embodiments, the protective gas is argon. The purity of argon is 99.999%. After degassing, argon is introduced into the sample chamber so that the pressure in the sample chamber is the first pressure. In an exemplary embodiment, the first pressure may be 5 to 13 kPa. For example, the first pressure may be 10 kPa. Hydrogenation is performed under a pressure of 10 kPa, and the pressure change during the hydrogenation process can be accurately detected, thereby ensuring the accuracy of the hydrogenation results. Under the second temperature condition, the pressure in the sample chamber is 10 kPa. In an exemplary embodiment, the second temperature may be 360°C to 450°C. For example, the second temperature may be 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, etc. A certain amount of pure hydrogen is introduced for hydrogenation when the pressure is 10 kPa and the temperature is a certain temperature between 360 and 450°C. The maximum hydrogen permeation temperature is 450℃, which is 30℃ lower than the minimum annealing temperature (480℃) in general, avoiding the recovery and recrystallization of some zirconium alloys and not changing the structure and properties of zirconium and zirconium alloys. The minimum hydrogen permeation temperature is 360℃, which can ensure the hydrogen adsorption rate and avoid the adsorption time being too long.

[0040] In some embodiments, the number of multiple hydrogenation can be 3-20 times. The target application amount is divided into 3-20 times. Multiple hydrogenation can accurately control the hydrogenation amount.

[0041] In some embodiments, the amount of pure hydrogen introduced in a single hydrogenation is 0.005 wt % to 0.0075 wt % in terms of hydrogen content.

[0042] In some embodiments, the volume V of pure hydrogen gas introduced in a single hydrogenation is obtained by the following formula:

[0043]

[0044] Wherein, V is the volume of pure hydrogen introduced, ml; M is the relative molecular mass of hydrogen; A is the hydrogen content of single hydrogenation, wt%; m is the weight of the sample, g.

[0045] The method and its effect of the present application are described below by specific examples. In the following examples, the hydrogen content obtained is tested by a hydrogen analyzer RH600 (LECO, USA). Each sample is tested twice and the average value is taken.

[0046] Example 1

[0047] The target hydrogen content is 0.07wt%. The sample is a CZ alloy plate, a δ0.5mm strip, and weighs 4g. The hydrogen content of pure hydrogen gas injected once is determined to be 0.007wt%, and a total of ten hydrogen permeations are performed. The single hydrogen filling volume is 313.6ml.

[0048] The CZ alloy sample was placed in the sample chamber of the hydrogen permeation device, and the vacuum degree in the sample chamber was controlled to be ≤1.0×10 -2 Pa, and then the temperature is raised. When the temperature rises to 440℃, it is kept at this temperature for 15 minutes for degassing. During the heating and keeping process, the vacuum degree changes slightly as the zirconium and zirconium alloy are degassed. Finally, the vacuum degree in the sample chamber is kept ≤1.0×10 -2 Pa.

[0049] After vacuum degassing, argon gas with a purity of 99.999% was introduced into the sample chamber. The pressure in the sample chamber was controlled to be 10 kPa and the temperature of the sample chamber was controlled to be 440°C.

[0050] Each time 313.6 ml of pure hydrogen was introduced, and when the pressure in the sample chamber returned to 10 kPa, the next hydrogenation was performed. A total of ten hydrogenation were performed to obtain a hydrogenated part.

[0051] Sample hydrogen content test results: 0.0695wt%.

[0052] Example 2

[0053] The target hydrogen content is 0.14wt% hydrogen permeation, the sample is Zr-4 alloy, δ0.6mm plate, weight 2.2g. Determine 19 times of hydrogen permeation, the single pure hydrogen introduced from 1 to 18 times is 0.0075wt% based on the hydrogen content, and the single hydrogen filling volume is 184.8ml. The 19th hydrogen permeation, the hydrogen introduction volume is 0.005wt%, and the last (19th) hydrogen filling volume is 123.2ml.

[0054] Place the zirconium alloy sample in the sample chamber of the hydrogen permeation device and control the vacuum degree in the sample chamber to ≤1.0×10 -2 Pa, and then heat up. When the temperature rises to 420℃, keep it warm for 10 minutes for degassing. During the heating and heat preservation process, the vacuum degree changes slightly as the zirconium and zirconium alloy degas. Finally, the vacuum degree in the sample chamber is kept ≤1.0×10 -2 Pa.

[0055] After vacuum degassing, argon gas with a purity of 99.999% was introduced into the sample chamber. The pressure in the sample chamber was controlled to be 10 kPa and the temperature of the sample chamber was controlled to be 430°C.

[0056] Each time 184.8 ml of pure hydrogen was introduced, and when the pressure in the sample chamber returned to 10 kPa, the next hydrogenation was performed, and a total of 18 hydrogenation were performed. When the pressure in the sample chamber returned to 10 kPa, 123.2 ml of pure hydrogen was introduced for the 19th hydrogenation. A hydrogenated part was obtained.

[0057] Sample hydrogen content test results: 0.1394wt%.

[0058] Example 3

[0059] The target hydrogen content is 0.02wt% hydrogen permeation, the sample is Zr-4 alloy pipe, the sample weight is 10.4g, the single pure hydrogen content is determined to be 0.005wt%, and the single hydrogen filling volume is 582.4ml. A total of four hydrogen permeations are performed.

[0060] Place the zirconium alloy sample in the sample chamber of the hydrogen permeation device and control the vacuum degree in the sample chamber to ≤1.0×10 -2 Pa, and then heat up. When the temperature rises to 400℃, keep it warm for 20min for degassing. During the heating and heat preservation process, the vacuum degree changes slightly as the zirconium and zirconium alloy degas. Finally, the vacuum degree in the sample chamber is kept ≤1.0×10 -2 Pa.

[0061] After vacuum degassing, argon gas with a purity of 99.999% was introduced into the sample chamber. The pressure in the sample chamber was controlled to be 10 kPa and the temperature of the sample chamber was controlled to be 400°C.

[0062] Each time 582.4 ml of pure hydrogen was introduced, and when the pressure in the sample chamber was restored to 10 kPa, the next hydrogenation was carried out, and a total of 4 hydrogenation were carried out to obtain a hydrogenated part.

[0063] Sample hydrogen content test results: 0.0202wt%.

[0064] Example 4

[0065] The target hydrogen content is 0.1wt% hydrogenation, the sample is a Zr-Sn-Nb alloy plate with a thickness of δ1.2mm and a weight of 14.6g, and a total of 15 hydrogenation. For the 1st to 14th hydrogenation, the pure hydrogen gas passed through the hydrogenation is 0.0067wt% based on the hydrogen content, and the single hydrogen filling volume is 1095.584ml. The pure hydrogen gas passed through the 15th hydrogenation is 0.0062wt% based on the hydrogen content, and the single hydrogen filling volume is 1013.824ml.

[0066] Place the Zr-Sn-Nb alloy plate in the sample chamber of the hydrogen permeation device and control the vacuum degree in the sample chamber to ≤1.0×10 -2 Pa, and then the temperature was raised. When the temperature reached 390°C, it was kept at this temperature for 25 minutes for degassing. During the heating and keeping process, the vacuum degree changed slightly as the zirconium and zirconium alloy degassed. Finally, the vacuum degree in the sample chamber was kept ≤1.0×10 -2 Pa.

[0067] After vacuum degassing, argon gas with a purity of 99.999% was introduced into the sample chamber. The pressure in the sample chamber was controlled to be 10 kPa and the temperature of the sample chamber was controlled to be 390°C.

[0068] 1095.584 ml of pure hydrogen was introduced each time. When the pressure in the sample chamber recovered to 10 kPa, the next hydrogenation was carried out. A total of 14 hydrogenation were carried out. For the 15th time, 1013.824 ml of pure hydrogen was introduced to obtain a hydrogenated part.

[0069] Sample hydrogen content test results: 0.1007wt%.

[0070] The above description is intended to be illustrative rather than restrictive. For example, the above examples (or one or more of them) can be used in combination with each other, and it is considered that these embodiments can be combined with each other in various combinations or arrangements. The scope of this application should be determined with reference to the attached claims and the full range of equivalent forms of these claims.

Claims

1. A method for hydrogenation of zirconium and zirconium alloys with quantitative hydrogen content, comprising: The zirconium or zirconium alloy sample is heated to a first temperature for degassing under a first vacuum condition; The first vacuum degree is not greater than 1.0×10 -2 Pa, the first temperature is 380°C to 450°C; Passing a protective gas, under a second temperature condition, the zirconium or zirconium alloy sample is placed in a protective gas atmosphere of a first pressure; the first pressure is 5 to 13 kPa, and the second temperature is 360° C. to 450° C.; A certain amount of pure hydrogen is introduced, and when the pressure returns to the first pressure, a certain amount of pure hydrogen is introduced again, and the hydrogenation is performed multiple times in a cycle until the total amount of pure hydrogen introduced reaches the target hydrogen content, and the temperature of the multiple hydrogenation processes is maintained at the second temperature; The amount of pure hydrogen gas introduced in a single hydrogenation is 0.005wt% to 0.0075wt% based on the hydrogen content; The volume V of pure hydrogen gas introduced in a single hydrogenation is obtained by the following formula: Wherein, V is the volume of pure hydrogen introduced, ml; M is the relative molecular mass of hydrogen; A is the hydrogen content of single hydrogenation, wt%; m is the weight of the sample, g.

2. The method according to claim 1, characterized in that The step of heating the temperature to the first temperature for degassing includes heating the temperature to the first temperature and keeping the temperature for 10 to 25 minutes for degassing.

3. The method according to claim 1, characterized in that The protective gas is argon.

4. The method according to claim 1, characterized in that: The number of multiple hydrogen permeation is 3-20 times.

5. A zirconium and zirconium alloy hydrogen-impregnated part with a quantitative hydrogen content, which is prepared by the method according to any one of claims 1 to 4.

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